Use of methylidyne bis pyrazolones for dyeing



United States Patent USE OF lVIETHYLIDYNE BIS PYRAZOLONES FOR DYEING Carl M. Smith, Easton, Pa., assignor to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware v No Drawing. Application August 5, 1954 Serial No. 448,133

17 Claims. (Cl. 8-55) This invention relates to a novel process for dyeing animal fibers and synthetic polymeric thermoplastic sheet and fibrous material, and more particularly to the use in such a process of methylidyne bis pyrazolones of the formula 0H=o-om wherein R and R are selected from the group consisting of lower aliphatic and rnonocyclic aromatic radicals, X is selected from the group consisting of O and S, Y and Y are selected from the group consisting of hydrogen, halogeno, lower alkoxy, lower alkyl and sulfonamido and n, and n are integers from'l to 2.

' The methylidyne bis pyrazolones of'the above formula are well known in the prior art, and may be made in a variety of manners. Compounds wherein X is oxygen may be prepared by reaction of 2 molecular equivalents of the desired S-pyrazolone components with '1 molecular equivalent of a methylidyne donor linking agent such as formamide, orthoformic acid or an acyloxydialkoxyformal or of chloroform and alkali. The symmetrical compounds obtained by reacting 2 molecular equivalents of the same 5-pyrazolone with the linking agent are in gen eral preferred. However, by reacting a mixture of two' dissimilar S-pyrazolones with the linking agent, an unsym-' metrical product is readily obtained in like manner. Compounds wherein X is sulfur may be prepared by reacting their'oxygenanalogs with phosphorus pentasulfide. It will be understood that the oxygen analogs may beprepared from the sulfur analogs by reaction with suitable agents under proper conditions. 7

In the formula given above, R and R may represent a lower aliphatic radical such as methyl, ethyl, trifluoro ducing the methylidyne. bis 'pyrazolones of the instant invention include l-(x-chlorophenyl)-3-methyl-5-pyrazolone, l-(x-bromophenyl) -3-methyl-.5-pyrazolone, -.1 (pa. Iolyl)-3-methyl 5pyltazolone, l -phenyl-.3.-,trifluoromethyl- Other suitable 5- pyrazolone components which may be employed in 'pro-,

ice.

5-pyrazolone, lone, 1-(m-[N,N dimethyl]sulfamylphenyl)-3-methyl 5- pyrazolone, 1 (m [N-morpholino]sulfamylphenyl)3 methyl-S-pyrazolone, l (x-chlorophenyl)-3-carbomethoxy-5-pyrazolone, 1-phenyl-3-carboethoxy-S-pyrazdlone, and the sulfur analogs of these compounds, and the like.

The methylidyne bis pyrazolones above described have hitherto been employed as indicators and as sen's'itizers dyeing textile .or synthetic polymeric thermoplastic material. As a matter of fact, the closely related compound rubazonic acid, wherein the methylidyne linkage is replaced by a -'N: linkage, produces dyeings on Dacron which are extremely fugitive, fading to a clean white after two hours in the Fadeometer. It was accordingly, unforeseeable and highly unexpected to discover that the methylidyne bis pyrazolones above described may be employed for dyeing animal fibers and synthetic polymeric thermoplastic material in sheet or fibrous form to yield yellow. dyeings having excellent lightand washfastness. The reason for this surprising behavior is not known, but in any case, the process of this invention enables the production of yellow dyeings of a highly improved and stable character hitherto difiicult to attain.

The material which may be dyed in accordance withv the process of this invention may have a basis of animal fibers such as wool or silk, or of synthetic polymeric thermoplastic material such as polyacrylonitrile, polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride,

polyethylene terephthalate, nylon, cellulose acetate, or

mixtures and copolymers thereof. All the aforementioned.

synthetic polymeric thermoplastic materials are representative of those which are 'at least as hydrophobic as cellulose acetate and are dyeable in known manner with disperse dyestufis. As representative of readily available synthetic material which may be dyed in accordance with the process of this invention, there may be mentioned Dacron (polyethylene terephthalate), Orlon and Acrilan (at least percent polyacrylonitrile), Dynel and Vinyon a N (acrylonitrile-vinyl chloride copolymer), Vinyon.

(vinyl acetate -vinylchloride copolymer), Saran v (polywarps, fabrics, felts and the like and treated as a wound package, running lengths, fibrous stock, bulk, etc. 7

In carrying out. the process of this invention, the

methylidyne bis pyrazolones may be employed in pro-' portions of from about 0.02 to 5% by weight of the material being dyed, depending upon the desired depth The usual methods of dyeing may be made of shade.

use of. Preferably, the dye is .applied as a disperse dyestuff in; the form of its dispersion in a liquid media, It will be understood that the term dispersion. ein-" ployed herein is used in its broad sense tofinclude suspensions,,emulsions or solutions of the instant compounds in liquid organic or inorganic media in concentrations obviously 1 determined. by the depthof shade desired} duration and type of treatment (as by exhaustion orf otherwise), material being dyedandthe like. 2 1

Completely acceptable results may be obtained by ap-fi plication from aqueous dispersion with theaidof rurl'fac'ei= 1- (m-sulfamylphenyl) -3 -methyl 5-pyrazo-" active assistants and dispersing agents, and/or carriers such asbenzoic acid, m-cresol, phenol, salicylic acid, orthoand para-phenylphenol,phenylmethyl carbinol, andjthe like Dye powdercompositions comprising by weight about .20 to 80 partsfof' "theLmethylidyne bis pyraz-' oloneand about80 to 20 partsiof a finely divided dispersing agent have'beenfound to'be highly suitable forj to the aqueous dispersion employedfor dyeing. For.

certainniaterials such as Dacron and the; like, application ofthe'aqueous dye composition in the presence of a one of the above-mentioned .carriers enables the attainment of improved dyeings.

Excellent results .maybe. obtained. by applying the methylidyne bis pyrazolone from a solution thereof in an organic solvent, as for example polyhydric alcohols such as ethylene glycol, propylenetglycol, 1,4.butanediol, 1,2,4- butanetriol, and especially diethylene glycol and the like,

at temperatures of about 170 to 190C. for a short period of time of theorder of about to 20 seconds.

The requirements of the latter process with .respectto solubility and'stability atthe temperatures employed, in

addition to the production of light-g and, wash-fast dye.-

ings have been found, to be satisfactorily fulfilledbythe compounds employed in the process'of this invention.

If desired, synthetic polymeric thermoplasticrnaterial.

in any desiredform may be dyed by incorporation of the methylidyne bis pyrazolones' of this invention,..into the compositions from which they are formed, as for. example into the spinning solutions, molding compositions and the like. Thus colored acetate rayon or film may be obtained by incorporation of the methylidyne bis pyrazolone into thespinning solution from which the film or fiber is shaped or extruded.

The following examples, in which parts are by weight unless otherwise indicated',' 'are illustrative but not limitative oi the instant invention.

' ";-EXAMPLE 1 0.025 g. 4,4'-rnethylidyne bis (l'-phenyl-3-methyl-5- pyrazolone) was dissolved in a heated mixture of 2 cc. alcohol and 4 cc. acetone. There was then added 2 cc.

Igepon T (sodium N-acylN-alkyltaurateiin 5% aqueous solution) and about 100 cc. hot water followed by 100 cc.-Glaubers salt solution) and 10 'cc.acetic acid (1.4% aqueous solution); This dispersion was brought up to 300 cc. volume with water. A 5 g. sample of pre wet fiber was dyed in vthedispersion at the boil for 1 hour, rinsed. and dried.

Dyeing an Dacron.-Dyestutf exhausted well from the bath and gave greenish-yellow dyeings of excellent wash and light fastness. V

Dyeing on Dyne!.-Dyestuif exhausted well from the bath and gave strong greenish-yellow shades of excellent, wash and good light fastnessa The fiber may be relustered in 6% NaCl solution for 10 minutes atthe boil before drying. r

a EXAMPLE 2 I a 0.014 g., dyestufi mixture containing 50 parts 4,4- methylidyne bis (1-phenyl-3-methyl-5-pyrazolone) and SOparts Tamol NNO (condensation product of formaldehyde' and naphthalene sulfonic acid) was mixed with 100 cc. acetic acid (1.4% aqueous solution) and the dispersion brought up to 300 cc. volume with water. A 5

g. sample-of acetaterayon fabric was dyed in the dis-j persion for ldhour' at 190 F., the-goods"being entered 4 EXAMPLE 3 r 0.05 g. dyestufr' mixture as in Example 2 was pasted with 2 cc. IgepOn T (5% aqueous solution) in a small beaker, and about 50 ccwarm water were added. 5 g. swatches of acetate rayon and. pro-wet Dacron were worked 5-7 minutes at 180 F. in 200 cc. of distilled water-:containirig '4 gbenzoic acid. To this beaker, the

dispersion of dyestuif was then added and volume brought up to 300 cc. with distilled water. The dyebath was maintained for 1 /2 hours at the boil, after which the swatches were rinsed well. I

The dyestuff exhausted completely from the bath and the dyeings were a strong bright greenish-yellow of excellent light, crocking, and wash fastness with good sublimation fastness (1 minute at 320 F.). Color strength increased on AATCC Wash Test #3 with the acetate swatch.

' EXAMPLE 4 0.05 g. 4,4'-methylidyne bis (l-pheny1-3-methyl-5- pyrazolone) was brought intosolution in 10 cc. diethylene glycol by heating to 190-l95 C. At 180 C. a 0.05 g. swatch of Dacron was entered, stirred vigorously for 10 secondsiin the solution, removed and immediately plunged into cold water. Then the dyed swatch was soaped by hand, rinsed and dried. Dyeing was a bright strong greenish-yellow, of excellent wash and light fastness (100 hour Fadeometer test).

" EXAMPLE 5 0.05 g. 4,4-methylidyne bis (1,3-diphenyl-5-pyrazolone) was-brought'into solution in 10 cc. diethyleneglycol by heating to 1 90- 195 C. At 180 C. a 0.5 g. swatch of Dacron was entered, stirred vigorously for 10 seconds in the solution, removed and immediately plunged into cold water Then the dyed swatch was soaped by hand, rinsed and dried. Dyeing was a bright strong greenish-yellow of excellent wash and light-fastness (100 hour Fadeorneter test).

EXAMPLE 6 To a solution of '15 g. of 4,4'-methylidyne bis (1 phenyl-3-methyl-5-pyrazolone) in 250 cc. of chloroform was slowlyadded with stirring, 13.4 g. of bromine.v The mixture was refluxed for two hours. Methanol was added and, the mixture refluxed for one hour, then chilled in an ice-bath. The yellow precipitate was recovered by filtration and air dried to form 10.5 g. ofyellow dye EXAMPLE 7 A mixture .of 36 grams of 4,4'-methylidyne bis (1- phenyl-3rmethyl'fipyrazolone), 300 cc. chlorobenzene and 0.5 cc. thionyl chloride was heatedto -70 with stirring. Over a periodfof 1% hours, a mixture of 28.5 'cc. sulfuryl chloride, 0.5 cc. thionyl chloride and 50 cc. chlorobenzene was added dropwiseito the mixture. The mixture was then stirred for 1 hour at and added to 1 liter of coldwater. Sodium carbonate was added until the mixture was. alkaline, the chlorobenzene; was removed by steam distillation, and the yellow dyestutf precipitate recoveredby filtration.v I a a The "dyeing procedure of Example '3 was repeated,

except that the dyestufi employed was the corresponding chlorinatedproduct prepared as above. Bright yellowishgreen dyeings with goodexhaust were. obtained. Light,

crocking and wash-fastness were excellent. Testing at 320 F. for one minute showed good sublimation fastness. Color strength improved on AATCC Wash Test #3 on the acetate swatch.

This invention has been disclosed with respect to several preferred embodiments, and various modifications and variations thereof will become obvious to the person skilled in the art. It is to be understood that such modifications and variations are to be included within the spirit and purview of this application and the scope of the appended claims.

I claim:

1. A process comprising dyeing synthetic polymeric thermoplastic material with a compound of the formula wherein R and R are selected fiom the group consisting of lower aliphatic and monocyclic aromatic radicals, X is selected from the group consisting of O and S, Y and Y are selected from the group consisting of hydrogen, halogeno, lower alkoxy, lower alkyl, and sulfonamido, and 11 and n are integers from 1 to 2, dispersed in a liquid medium.

2. A process as defined in claim 1 wherein said compound is dispersed in an aqueous medium.

3. A process as defined in claim 1 wherein said compound is dissolved in an organic solvent medium.

4. A process as defined in claim 1 wherein said compound is dissolved in diethylene glycol.

5. A process as defined in claim 1 wherein said compound is 4,4-methylidyne bis (l-phenyl-3-methyl-5-pyrazolone) 6. A process as defined in claim 1 wherein said compound is 4,4-methy1idyne bis (1,3-diphenyl-5-pyrazolone).

7. A process as defined in claim 1 wherein said fibrous material has a basis of polyethylene terephthalate.

8. A process as defined in claim 1 wherein said fibrous material has a basis of cellulose acetate.

9. A process as defined in claim 1 wherein said fibrous material has a basis of a copolymer of acrylonitrile and vinyl chloride.

10. A dye powder composition comprising by weight about 20 to 80 parts of a finely divided dispersing agent and 80 to 20 parts of a compound of the formula 6 wherein R and R are selected from the group consisting of lower aliphatic and monocyclic aromatic radicals, X is selected from the group consisting of O and S, Y and Y are selected from the group consisting of hydrogen, halogeno, lower alkoxy, lower alkyl, and sulfonamido, and n and n are integers from 1 to 2.

11. A composition as defined in claim 10 wherein said compound is 4,4-methylidyne bis (l-phenyl-B-tnethyl-S-pyrazolone) 12. A composition as defined in claim 11 wherein said dispersing agent is the condensation product of formaldehyde and naphthalene sulfonic acid.

13. A composition as defined in claim 12 containing about equal amounts of said agent and said compound.

14. Synthetic polymeric thermoplastic material dyed with a compound of the formula fibrous material has a basis of polyethylene terephthalate.

16. A product as defined in claim 14 wherein said fibrous material has a basis of cellulose acetate.

17. A product as defined in claim 14 wherein said fibrous material has a basis of a copolymer of acrylonitrile and vinyl chloride.

References Cited in the file of this patent UNITED STATES PATENTS 2,028,141 Ackermann Jan. 21, 1936 2,031,356 Ackermann Feb. 18, 1936 2,032,502 Rod Mar. 3, 1936 OTHER REFERENCES American Dyestufi Reporter for Nov. 23, 1953, page P792.

American Dyestufi Reporter, Nov. 22, 1954, pp. 774- 779 (Article by Rhode Island Section). 

1. A PROCESS COMPRISING DYEING SYNTHETIC POLYMERIC THERMOPLASTIC MATERIAL WITH A COMPOUND OF THE FORMULA 